Herbicidal compositions and methods employing 3-(3, 4-dichlorophenyl)-1-methyl-1-methoxyurea with 3-amino-1, 2, 4-triazole



United States Patent HERBICIDAL COMPOSITIONS AND METHODS EM- PLOYING 3-(3,4-DICHLOROPHENYL)-l-METHYL- l-METHOXYUREA WITH 3 AMINO 1,2,4 TRI- AZOLE I Rayner S. Johnson, Carrcroft, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Apr. 30, 1965, Ser. No. 452,371

' 2 Claims. (Cl. 71-2.5)

This application is a continuation-in-part of my copending application Ser. No. 301,981, filed Aug. 14, 1963,

which is a continuation-in-part of my application Ser. No. 64,254, filed Oct. 24, 1960, both now abandoned, which was a continuation-in-part of my application Ser. No. 733,213, filed May 5, 1958, now abandoned.

This invention relates to compositions useful as herbicides. It is more particularly directed to herbicidally effective compositions containing a herbicidal methoxy phenyl urea compound together with another herbicidally active compound.

The search for herbicidally effective compositions continues. No single herbicidal composition is known that performs as effectively as needed or as desired under conditions favorable to the growth of undesired vegetation.

According to the present invention, a surprisingly effective herbicidal compositionhas been discovered that comprises two essential ingredients:

(1) A methoxy phenyl urea of the formula where X is hydrogen or halogen, preferably chlorine:

n is 1, 2 or 3;

Y is hydrogen, alkyl of less than carbons, or alkoxy of less than 5 carbons, provided that X is not chlorine when Y is alkoxy or alkyl of 2 through 4 carbons;

m is l or 2;

R is hydrogen or alkyl of less than 5 carbons, preferably hydrogen or methyl;

R is hydrogen or alkyl of less than 5 carbons, preferably methyl; and

R is alkyl of less than 5 carbons, preferably methyl;

together with- (2) at least one second herbicidally active compound in an amount for each ten parts by weight of said methoxy phenyl urea, of the following indicated amounts of the following listed compounds:

HERBICIDE Ureas Parts 3-(p-chlorophenoxyphenyl) 1,1 dimethylurea 2-60 3 3 ,4-di'chloropheny1)-1,1-dimethylurea 2-3 0 3- (4-chlorophenyl) -1, l-dimethylurea 2-3 0 3-phenyl-1,l-dimethylurea 2-30 3-(3,4-dichlorophenyl) l-n-butyl-l-methylurea 2-30 3-(3,4-dichlorophenyl) 1,1,3 trimethylurea 2-30 HERBICIDE-Continuea' Phenols Sodium dinitrocresylate Dinitro-sec.-butylphenol and salts thereof Pentachlorophenol and salts thereof Carboxylic acids and derivatives 3-amino-2,5-dichlorobenzoic acid and salts thereof S-nitro-2,5-dichlorobenzoic acid and salts thereof 2-meth-yl-3,-dichlorobenzoic acid and its salts 2,3,6-trichlorobenzyloxypropanol 2-methoxy-3,5,6-trichlorobenzoic acid and salts thereof 2-methoxy 3,6-dichlorobenzoic acid and salts thereof 2,6-dichlorobenzonitrile 2,4-dich1orophenoxyacetic acid and salts and esters thereof 2,4,S-trichlorophenoxyacetic acid and salts and esters thereof (2-methyl-4-chlorophenoxy)acetic acid and salts and esters thereof 2-(2,4,5 trichlorophenoxy)propionic acid and'salts and esters thereof 2-(2,4,5 trichlorophenoxy)ethyl 2,2-dichloropropionate 4-(2,4-dich1orophenoxy)butyric acid and salts and esters thereof 4-( 2-methyl-4-chlorophenoxy butyric acid and salts and esters thereof Trichloroacetic acid and salts thereof 3,4-dichloromethylacrylanilide 3,4-dichloropropionanilide N-phenylcarbamic acid, isopropyl ester N-(m-chlorophenyl)carbamic acid, isopropyl ester N-(m-chlorophenyl)carbamic acid, 4-chloro-2-butynyl esters Maleic hydrazide Triazines 2-isopropy1amino 4 methoxyethylamino-6 methylmercapto-s-triazine 2-methylmercapto-4,6-bis isopropylamino) s-triazine 2-methylmerctapto 4,6-bis(ethylamino)-striazine Z-methylmercapto 4-ethy1amino-6-isopropylamino-s-triazine 2-methoxy-4,6-bis(ethylamino)-s-triazine 2-chloro 4,6-bis(metho xypropylamino)-striazine 2 methoxy 4,6 bis(isopropylamino)-'striazine 2-methoxy-4-ethylamino-6-isopropylaminos-triazine 2-ch1oro 4,6 bis(isopropylamino)-s-triazine 3,322,527 Patented May 30, 1967 Parts 3 HERBICIDE-Continucd Inorganic and mixed inorganic-organic salts Parts Calcium propylarsonate 2-1600 Disodium monomethylarsonate 7.5-400 Dimethylarsinie acid 7.5-400 Polyborochlorate 900-32,000 Ammonium thiocyanate 2.5-40 Octyl-dodecylammonium methylarsonate 7.5-400 Sodium arsenite 4-300 Lead arsenate 3200-l30,000 Calcium arsenate 1600-65,000 Sodium tetraborate hydrated, granulated 900-32,000 Sodium metaborate 900-32,000 Sodium pentaborate 900-32,000 Unrefined borate ore such as borascu 900-32,000 Sodium chlorate 2.5-2000 Ammonium sulfamate 4-800 5,6-dih-ydro(4A,6A) dipyrido-(l,2-A,2,1'-

C)-pyrazinium dibromide .1-240 Others 3-amino-l,2,4-triazole 2.5-40 3,6-endohexahydrophthalic acid 2.5-40 Hexachloroacetone 2-1600 Diphenylacetonitrile -100 N,N-di(n-propyl) 2,6 dinitro-4-trifiuoromethylaniline 5-40 O-(2,4-dichlorophenyl) O methyl-isopropylphosphoroamidothioate S-400 2,3,5,6-tetrachloroterephthalic acid, dimethyl ester 5-300 2,4-dichloro-4'-nitrodiphenylether 0.5-60 Chlordan -600 l,l'-dimethy1-4,4 dipyridylium di-(methyl sulfate) 0.1-240 N,N-di(n-propyl) 2,6 dinitro-4-rnethylaniline 5-60 The novel herbicidal compositions of the present invention should contain herbicidally effective amounts of the methoxy phenyl urea and of the other compound or compounds from the above list. The relative proportions of the two can be varied considerably depending on the particular use. The herbicidally active components can be used with various conditioning agents and adjuvants in a customary manner as will be described below. Ordinarily, one would not use less than about 2% of the active ingredient in, say, granular compositions while in waterdispers-able powders or solutions adapted to be dispersed further, compositions may contain up to 80%, 90%, or even more of the active components.

Herbieidal compositions of the invention are prepared by admixing the substituted alkoxy urea and the other herbicide in herbicidally effective amounts, with conditioning agents of the kind used and referred to in the art as pest control adjuvant or modifier to provide formulations adapted for ready and efiicient application to soil or weeds (i.e. unwanted plants) using conventional applicator equipment.

Thus the herbicidal compositions or formulations are prepared in the forme of solids or liquids. Solid compositions are preferaby in the form of dusts and are compounded to give homogeneous free-flowing dusts by admixing the active compound with finely-divided solids, preferably tales, natural clays, pyrophyllite, diatomaceous earth or flours such as walnut shell, wheat, redwood, soybean, cotton seed flours and other inlet solid conditioning agents or carriers of the kind conventionally employed in preparing pest control compositions in dust or powder form.

Liquid compositions of the invention are prepared in the usual way by admixing the substituted urea with a suitable liquid diluent media. With certain solvents such as alkylated naphthalene, dimethylformamide and cresol,

relative high, up to about 35% by weight or more, concentrations of the active urea compound can be obtained in solution. Other liquids conventionally used in preparing liquid herbicidal compositions can also be used.

The herbicidal compositions of the invention whether in the form of dusts or liquids preferably also include one or more surface-active agents of the kind sometimes referred to in the art as a wetting, dispersing or emulsifying agent. These agents which will be referred to hereinafter more simply as surface-active dispersing agents cause the compositions to be easily dispersed in water to give aqueous sprays which for the most part constitute a desirable composition for application.

The surface-active agents employed can be of the anionic, cationic or non-ionic type and include, for example, sodium or amine salts of alkyl benzene sulfonates, and sulfated fatty alcohols, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, acetylinie glycols, methyl cellulose, polyvinyl alcohol, polymeric akyl naphthalene sulfonates, sodium naphthalene sufonate, poymethylene bisnaphthalenesulfonate and sodium-N- methyl-N-(long chain acid)taurates, alkyl aryl polyethoxy alcohols, alkyl polyethoxy alcohols, polyoxyethylene sorbitol or sorbitol fatty acid esters, polyethylene glycol fatty esters, fatty alkylol amide condensates, sodium and potassium oleate, the amine salts of oleic acids such as morpholine and dimethylamine ehelates, the sulfonated animal and vegetable oils such as sulfonated fish and eastor oils, sulfonated petroleum oils, sulfonated acyclic hydrocarbons, sodium salt of lignin sulfonic acid (goulae), alkyl naphthalene sodium sulfonate and other wetting, dispersing and emulsifying agents such as those listed in detail by Detergents and Emulsifiersl964 Annual by John W. McCutcheon, Inc.

Generally the surface-active agent will not comprise more than about 5 to 15% by weight of the composition depending, of course, upon the particular surface-active agent, the system in which it is placed, and the result desired, and in certain compositions, the percentages will be 1% or less. Usually the minimum lower concentration will be 0.1%.

Additional surface-active agents can be added to the above formulation to increase the ratio of surface-active agent:active agents up to as high as 5:1 by weight. The addition of higher rates of surface-aetive agent increases the herbicidal effect of the active compounds. When used at high rates, it is preferred that the surface-active agents be present in the range of one-fifth to five parts surfactant for each one part of active agent.

The herbicidal compositions are applied either as a spray, granule, pellet, or a dust to the locus or area to be protected from undesirable plant growth, commonly called weeds, i.e., plants growing where they are not wanted. Such application can be made directly upon the locus or area and the weeds thereon during the period of weed infestation in order to destroy the weeds but, if desired, the application can be made in advance of an anticipated weed infestation to prevent such infestation. Thus the compositions can be applied as aqueous foliar sprays and can also be applied as sprays directly to the surface of the soil. Alternatively, the dried powder compositions can be dusted directly on the plants or on the soil. Application of granules is an efiective method for obtaining pre-emergence control of weeds with minimum injury to foliage of desired growing plants. Application of pellets, either by hand or by machine applicators, e.g., by airplane, is an effective method for obtaining complete kill of undesired brush growth in fence rows, under power lines, etc.

The active compounds are, of course, applied in amounts suflicient to exert the desired herbicidal action. The amount of the herbicidally active ingredients present in the compositions as actually applied for destroying, preventing, or controlling weeds will vary with the manner of application, the particular weeds for which control is sought, the purposes for which the application is being made, and like variables. In general, the herbicidal compositions as applied in the form of a spray, granule, pellet, or a dust will contain from about 0.5% to 85% by weight of herbicidally active ingredients.

. Fertilizer materials, other herbicidal agents, and other pest control agents such as insecticides and fungicides can be included in the herbicidal compositions of the invention, if desired.

Compositions and methods of the invention are illustrated by the following examples. The indicated percentages are by weight.

Example 1 Percent 3-(3,4-dichlorophenyl)-1,1-dimethylurea 40.00 3-(3,4-dichlorophenyl)-1 methoxy-1-methylurea 40.00 Alkyl naphthalene sodium sulfonate 1.75 Low viscosity methyl cellulose 0.25 Attapulgite clay 18.00

Example 2 Percent 3-(3,4-dibromophenyl)-l-methoxy-l-methylurea 14.00 2 chloro 4,6 bis(methoxypropylamino)-s-triazine 14.00 Sodium lignin sulfonate 15.00 Hydrated attapulgite 1.75 Sodium pentachlorophenate 0.70 Disodium phosphate 0.90

Water 53.65

The above components are mixed together and pebble milled or sand milled until the insoluble components are substantially all below 5 microns in particle size. This formulation is used at the rate of 3 pounds of total active ingredients per acre in 40 gallons of water for both preand directed post-emergence weed control in sugar cane, corn, sansevieria and asparagus. The seedling weeds present in the growing crops are killed and good residual weed control is obtained. Crabgrass, foxtail, junglerice grass, seedling grass, pigweed, velvetleaf, flower-of-an-hour and many related weeds are controlled with no visible injury to the crops. At the rates of 20 pounds of total active ingredients per acre, good industrial weed control is obtained on weeds growing around oil tanks. A particularly important feature of this mixture is outstanding control of hard-to-kill broadleaf and perennial weeds, including quackgrass, plantain, dandelion, chickweed, crabgrass, marestail and goldenrod.

I Example 3 Percent 3-(4-bromophenyl)-l-methoxy-1-methylurea 1O 2 (2,4,5 trichlorophenoxy)propionic acid, sodium salt Attapulgite clay 85 The above components are mixed together and micropulverized, then moistened with water and moist granulated, followed by drying to yield a granular :product. This formulation is applied at the rate of 22.5 pounds of herbicidally active ingredients per acre with a specially adapted granular spreader to an infestation of Virginia creeper, trumpet vine, wild carrot, pigweed, oxeye daisy, crabgrass, bluegrass and lovegrass. Excellent weed control is obtained.

6 Example 4 Percent 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea 60.0

The above composition is blended and micropulverized until substantially all particles are below 50 microns.

A solution of 2,4-dichlorophenoxyacetic acid, dimethylamine salt containing 4 pounds of acid per gallon of water is prepared separately.

The above two compositions are combined in a tank mix at the rate of 10 pounds of the urea composition and one-half gallon of the 2,4-dichlorophenoxyacetic acid solution per 160 gallons of spray. Forty gallons of this spray mixture are applied to emerged weeds in corn which is 5 to 12 inches tall. Excellent control is obtained of crabgrass, giant foxtail, barnyard grass, chickweed, Pennsylvania smartweed, sunflower and jimsonweed, with no visible injury to the corn.

Example 5 Percent 3 (3-bromo-4-methylphenyl)-l-methoxy-1-methylurea 50.00 Trichloroacetic acid, sodium salt 25.00 Dodecylbenzenesulfonic acid, sodium salt 1.75 Sodium lignin sulfonate 1.00 Diatomaceous silica 22.25

The above components are blended and micropuverized until substantially all particles are below 50 microns.

This mixture is applied at the rate of 45 pounds of herbicidally active ingredients per acre in gallons of water for the control of a mixed vegetation of grasses and broadleaves growing under power line transformers. Excellent control is obtained of quackgrass, crabgrass, broomsedge, giant foxtail, barnyard grass, pigweed, blackeyed susan, chickweed and evening primrose.

Example 6 Percent 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea 4 Chloroisopropyl-N-phenyl carbamate 20 Xylene 66 Oil soluble petroleum sulfonates 10 Example 7 Percent 3-(3,4-dibromophenyl)-1-methoxy-1-methylurea 1 N-(m-chlorophenyl)carbamic acid, 4-chloro-2-butynyl ester 3 Attapulgite clay 96 The above components are first blended, then moistened with water, granulated and dried. Granules of 15-30 mesh are applied for weed control and are particularly effective for pro-emergence weed control in corn, soybeans, sansevieria, and gladiola. One hundred pounds of the formulation is applied with a granular spreader mounted on a tractor. This treatment gives control of a wide variety of annual broadleaf and grass weeds, including crabgrass, pigweed, lambsquarters, giant foxtail, barnyard grass, velvetleaf, chickweed and cockleburr.

Example 8 Percent 3-(3,4-dichlorophenyl)-l-metl1oxy-l-methylurea 50 5,6-dihydro (4A,6A)dipyrido (1,2-A,2',1-C)-pyrazinium dibromide 1O Polyoxyethylated nonyl phenol (7 mols ethyl oxide 1 Attapulgite clay 39 The above wettable powder is prepared by blending the components and grinding until substantially all particles are below 50 microns.

This formulation is applied at the rate of 18 pounds of total active ingredients per acre. Quick kill of a wide variety of broadleaf and grass weeds is obtained along fence rows. Among the many weeds that are controlled are bluegrass, crabgrass, broomsedge, foxtail, goldenrod, pigweed, seedling Johnson grass and plantain.

Example 9 Percent Sodium metaborate-hexahydrate 55.0 Sodium chlorate 36.6 3-(p-chlorophenyl)-1-metl1oxy-1-methylurea 8.4

The above composition is prepared in granular form as follows:

Fifty and eight tenths parts sodium metaborate pentahydrate in granular crystalline form is mixed with a paste of 8.4 parts of powdered urea herbicide and 4.2 parts of water. As mixing continues, the water is taken up to form the hexahydrate and the urea remains firmly adhering to the crystalline mass. This composition is then blended with 36.6 parts of granular sodium chlorate to yield the final composition.

This formulation is applied at the rate of 15200 pounds of total active herbicidal ingredients per acre for control of weeds around electric power line towers. Excellent control is obtained of broadleaf and grass weeds, including quackgrass, crabgrass, needlegrass, foxtail, watergrass, blackeyed susan, pigweed and marestail.

Example 10 Percent 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea 7.5 3,4-dichloromethacrylanilide 15.0 Xylene 71.5

Mixed polyoxyethylene ethers and oil soluble petroleum sulfonates Example 11 Tank mix combination with ammonium sulfamate-oil:

Percent (A) 3 (3,4-dichlorophenyl)-1-methoxy-1-methylurea 60.0 Alkyl naphthalene sodium sulfonate 1.5 Attapulgite clay 37.5 Low viscosity cellulose 1.0

8 This composition is prepared by blending and grinding the components until substantially all particles are below 50 microns.

(B) 5.32 pounds of ammonium sulfamate are dissolved in water and made up to a volume of 1 gallon.

The tank mix combination is prepared as follows:

Step 1.-Add 12 pounds of composition A to 90.6 gallons of water in a spray tank with agitation.

Step 2.When the solids are well wetted and dispersed, add 4 gallons of composition C, maintaining good agitation.

Step 3.Add 5.4 gallons of composition B slowly, while maintaining good agitation.

Since the oil emulsion in this mixture is relatively unstable and quick breaking, the order of mixing must be that described to avoid greasing out of a mixture of compositions A and C.

One hundred gallons of the spray mixture, mixed as described above, is applied along a railroad right-of-way for control of seedling woody plants and annual weeds. Excellent control is obtained of oak, maple, ash, elm, crabgrass, ragweed, foxtail and seedling Johnson grass.

Example 12 Percent 3-(3,4-dichlorophenyl)-1-methoxy-1-rnethylurea 60.0 Alkyl naphthalene sodium sulfonate 1.5 Methyl cellulose 0.5 Attapulgite clay 38.0

The above composition is blended and micropulverized until substantially all particles are smaller than 50 microns.

A solution of one pound N,N-di(n-propyl)-2,6-dinitro- 4-trifluoromethylaniline in 60 gallons of water is prepared separately.

The above two compositions are combined in a tank mix so that there is one pound each of the active urea compound and the trifiuoromethylaniline compound in gallons of water. Sixty gallons of this mixture are sprayed pre-emergence on an acre of cotton. Excellent control is obtained of annual weeds including mustard and other crucifers, with no injury to the cotton.

Example 13 Percent 3-(3,4-dichlor0phenyl)-l-methoxy-methylurea 14.00 3-amino-1,2,4-triazole 14.00 Sodium lignin sulfonate 15.00 Hydrated attapulgite 1.75 Sodium pentachlorophenate 0.70 Disodium phosphate 0.90 Water 53.65

The above components are mixed together and sandmilled until the insoluble components are substantially all below 5 microns in particle size. This formulation is sprayed at a rate of 1 pound of total active herbicidal ingredients per acre in 60 gallons of water in an area used for corn production that is heavily infested with quackgrass.

The quackgrass is completely eliminated in the sprayed area and corn subsequently produced from the area is not injured.

The invention claimed is:

1. A herbicidal composition comprising a herbicidally effective amount of a mixture of 10 parts by weight of 3-(3,4-dichlorophenyl)-1-methyl-1-methoxyurea and from 2.5 to 40 parts by weight of 3-amino-l,2,4-triazole.

2. A method for the conrol of weeds comprising applying to a locus to be protected 21 herbicidally etfective amount of a composition comprising a mixture of 10 parts by weight of 3-(3,4 dichlorophenyl-l-methyl-lmethoxyurea and from 2.5 to 3-amino-1,2,4-triazole.

References Cited UNITED STATES PATENTS 10 3,150,954 9/1964 Wheller 712.5 40 parts by weight of 3,152,880 10/1964 Weed 712.5

OTHER REFERENCES 5 German printed application 1,062,059, Steinbrum et 211., July 1959.

LEWIS GOTTS, Primary Examiner. cerereta.

Smathers X E. Examiner.

Luckenbaugh 712.6 X 10 JAMES O. THOMAS, JR., Assistant Examiner. 

1. A HERBICIDAL COMPOSITION COMPRISING A HERBICIDALLY EFFECTIVE AMOUNT OF A MIXTURE OF 10 PARTS BY WEIGHT OF 3-(3,4-DICHLOROPHENYL)-1-METHYL-1-METHOXYUREA AND FROM 2.5 TO 40 PARTS BY WEIGHT OF 3-AMINO-1,2,4-TRIAZOLE. 